Preparation of organic derivatives of tin



' citizen of the Republic of Switzerland, re-- assa s. s, 1926. UNITED STATES- 1,573,738 PATENT OFFICE.

cam:- o, or rams, niancn, assre'noa 'ro nranmssmrnms rournnc mans, or rams, raancn.

rmmrfon or oneamcnnnrva'rrvns or rm.

Drawing.

'Toall whom it may concem:

Be it known that I,-CA'RL OEGHSLIN, a

siding at Paris, in the Republic of France, have invented certain new and useful Im- Brovements in the Preparation of Organic erivatives of Tin, of which the following isa specification.

J. Meyer (-B, demonstrate the formation of analkyl-stannonic acid in the reaction of methyl iodide upon-an aqueous solution of sodium stannite. More recently, Druce (J. Ch soc. 113, 715,; 119, 758; 1922, 1859) prepared other alkylstannonic acids by applyin this method to ethyl iodide, isopropyl iodi e and the like.

rved that another class' of aliphatic halides have the property of formmg organic derivatives of tin by their action upon stannite of sodium, these being the a 'phatic halohydrins, which contain, in the same'carbon chain, one or more halogens and one or more 'h'ydroxylgroupss I am aware of the facility with which the chlorhvdrins are saponified by sodium h droxide even in the diluted state, and also 0 the fact Iobse sodium hydroxide may further act upon the chlorhydrins with formation ofoxide derivatives. For this reason, nothin led one to suppose that the action between hydrins and sodium stannite would be di rected towards the substitution and not towards the saponification.

In consequence, the new organic derivatives of tin represent stannonic acids which contain upon the organic group one or more alcoholic functions.

. Themajor part of the new derivatives of tin are found to differ from the knownderivatives by their solubility in water.

They are more diflicult to isolate in the pure state; they are also much less stable,

than the alkyl-stannonic acids, and will decompose at relatively low temperatures and m t e presence of acids, and chiefly strong acids even in the cold state.

The sulphides of the hydroxyalkyl-stannonic acids have a white colour hke the -sulphides of the alkyl stannonic acids, but

while the former are relativel stable, the latter become rapidlyconve 1n the ence of acids .into sulphides or oxysulp 'des of tin. The same transformation appears to take place at relatively low temperatures.

Ewample' 1.-A solution of 225 grammes 16. 1442) was the first to e chlorres-,

' Application fled September. 4, 1924. Serial in. 735,87l).

of stannous chloride in 380 c. c. of water is added slowly and. without stirring to 500 c. c. of caustic soda solution at 36 B. which has been cooled by adding 300 grammes of me. When the same is dissolved, 80.5 grammes of ethylene chlorhydrin are poured in. The sta'nnous acid now disappears, and the new derivative is formed having the formula:

Hocmcmsaoma The reaction may be represented as follows:

HO-CHz-CHr-Cl-I-SHCI: (in alkaline so1ution)= ,o -H0-oH.-oH,-sn +no1' ONa On completing the.-reaction,- the product may be se arated in various ways. It is preferably lsolated in the form of its sulphuretted derivative, this being less soluble in water than the onginal substance. For this purpose, 1t is precipitated b chloride of barium,

then saturated with by rogen sulphide, neu- Whenwtreated in the'centrifugal apparatus gas which corresponds by volume to one equivalent of ethylene. Theresidue has a yellow colour and is free from'carbon. The

usual acids, even diluted, will decompose the same with disengagement of' gas.

EwampZe'2.A solution of 225 grammes of stannous chloride in 225 c. c. of water is slowly added to 500 c. c. of caustic soda solution at 36 B. After the same has been dissolved 155 grammes of mono-bromohydrin of glycerin is poured into the alkaline solution. The stannite of sodium now disap ars, with formation of dihydroxypro y stannonic acid, which may be separated 111' the form of. its sulphuretted derivative according to the method indicated in Example 1. The dihydroxy-propyl-thiostannonic acid is a white powder which is but slightly soluble in water and soluble in sodium carbonate and in free alkalies, and also in the usual acids, but it rapidly becomes decomposed in these solutions. No melting point is found, but the substance is decomposed by heat into oxysulphide of tin.

Having now particularly described and ascertained the nature of my said invention and in what manner the same is to be performed, I declare that what I claim is 1. T he process which comprises treating a chlorhydrin with stannous chloride in the presence of an alkali metal hydroxide.

2. The process which comprises treating a chlorhydrin with stannous chlor de in the presence of sodium hydroxide.

3. The process which comprises treating an ethylene chlorhydrin with stannous chlo ride in the presence of an alkali metal hydroxide.

4.- The process which comprises treating an ethylene chlorhydrin with stannous chloride in the presence of sodium hydroxide.

5. The process which comprises treating ethylene chlorhydrin with stannous chloride in the presence of an alkali metal hydroxide.

6. The process which comprises treating ethylene chlorhydrin with stannous chloride in the presence of an alkali metal hydroxide and isolating the product in the form of its stable sulphur derivatives by treating the precipitated hydroxy alkyl stannonic acid derivative with hydrogen sulphide.

7. As new products, hydroxy ethyl stannonic acids having the probable formula:

In testimony whereof I aflix my signature.

CARL OEOHSLIN. 

